GB2036779A

GB2036779A - Polyester disazo dyestuffs

Info

Publication number: GB2036779A
Application number: GB7939899A
Authority: GB
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1978-11-22
Filing date: 1979-11-19
Publication date: 1980-07-02
Also published as: CH649668GA3; FR2442256A1; FR2442256B1; GB2036779B

Abstract

When mixed with emulsifiers, disazo dyestuffs, claimed per se, which are free from sulphonic acid groups and ammonium groups and have the formula <IMAGE> wherein D represents H, alkyl or -(E-O)n-R, E represents alkylene, R represents H, alkyl, cycloalkyl, aralkyl, aryl or acyl, n represents 3 to 7, m represents 1 or 2 and I represents 0 or 1, and rings A, B and C may be naphthalene and may be further substituted with the proviso that at least one radical D represents -O-(EO)n-R, give dyestuff preparations which under dyeing conditions are in a liquid or dissolved form. The use of additional dispersing agents, protective colloids, levelling agents and carriers can therefore be dispensed with when dyeing polyester fibres.

Description

SPECIFICATION Polyether disazo dyestuffs The invention relates to disazo dyestuffs which are free from sulphonic acid groups and ammonium groups and have the formula

wherein D represents H, alkyl or-(E-O)-R, E represents alkylene, R represents H, alkyl, cycloalkyl, aralkyl, aryl or acyl, n represents 3 to 7, m represents 1 or 2 and I represents 0 or 1 and the said radicals and also the benzene rings A, B and C, which are optionally made up to naphthalene ring systems, can be substituted by non-ionic radicals customary in the chemistry of the azo dyestuffs and/or by COOH, with the proviso that at least one radical D represents O(EO)nR.

The radicals -OD and -COOD are directly linked to an aromatic C atom of the chromophoric system and are preferably located in one and the same nucleus. The radical COOD can also be bonded via a bridge member, for example -OCH2 or C2H4. Suitable non-ionic substituents are those which are indicated for the preferred dyestuffs mentioned below.

Examples which may be mentioned are: alkyl, alkoxy, halogen, carboxyl, alkoxycarbonyl, OH, aminosulphonyl, nitro, acylamino, CN or the radical -O(EO)nR The number of these and other substituents in the rings A, B and C and also in any desired aryl radicals is in general 0 to 3. Alkyl radicals and cycloalkyl radicals in general have at most one substituent. The CF3 group is an exception.

Preferred dyestuffs have the formula

wherein E, R and n have the abovementioned meaning and T represents H or a non-ionic substituent of the indicated type or COOH and r represents 1 to 3.

the polyether radical being bonded to the dyestuff radical in the indicated manner.

Suitable alkylene radicals E are straight-chain or branched and have 2 to 6 C atoms. Preferred radicals are: -CH2CH2- and -cH2CH2CH2CH2-.

Suitable alkyl radicals, mentioned in any connection, are those with 1 to 4 C atoms, which can be substituted by a CN, OH, alkoxy, alkoxycarbonyl, alkoxycarbonyloxy or alkylcarbonyloxy group or halogen. They can also be unsaturated, such as allyl and butenyl.

Preferred alkyl radicals are saturated, unbranched and unsubstituted alkyl radicals. The methyi radical is particularly preferred.

Suitable alkoxy radicals, mentioned in any connection (that is to say, for example, including alkoxycarbonyl radicals), likewise have 1 to 4 C atoms.

Within the scope of this invention, "halogen" is understood as meaning in particular F, Br and especially CI.

Suitable cycloalkyl radicals, in any context, are cyclohexyl and methylcyclohexyl.

Suitable aryl radicals, in any context, are in particular phenyl radicals, which can be monosubstituted to trisubstituted by halogen, alkoxy or alkyl.

Suitable aralkyl radicals, in any context, are especially benzyl and phenylethyl radicals, in which the phenyl radicals can be substituted as described above.

Suitable acyl radicals, in any context, are alkylcarbonyl, alkoxycarbonyl, alkylsulphonyl, arylcarbonyl, arylsulphonyl or -OCONV1V2, in which V1 and V2 denote hydrogen or C1-C4-alkyl.

Suitable aminosulphonyl groups are -SO2NV1V2.

Particularly preferred dyestuffs have the formula

wherein X represents H, C 1-C4-alkyl, C1-C4-alkoxy, OH, NO2, CN, CF3, F, Cl, Br, C1-C4- alkylcarbonylamino, C1-C2-alkoxycarbonylamino, p-hydroxyethyl or-O-(E1-O)'-, Y, represents H, C1-C4-alkyl, C1-C4-alkoxy or Cl, Y2 represents Y, or NHCO-C1-C4-alkyl, or together with Y represents a fused benzene nucleus, Y3 represents Y, Z represents Y1, p represents 1 or 2, n' represents 3 to 5 (preferably 4 to 5), R' represents C1-C4-alkyl or -CONV1V2, in which V, and V2 denote H or C1-C2-alkyl, and E' represents C2H4 or -(CH2)4.

Very particularly preferred dyestuffs are those of the formula (III) wherein X represents H, CH3, OCH3, OC2H5, OH, NO2, CH3CONH, CH3OCONH, C2H5-OCONH or Cl, Y, represents H, Y2 and Y3 represent H, OCH3, CH3 or Cl, Z represents H, CH3 or Cl, R' represents CH3 or C2H5 and E' represents -CH2CH2-.

Compounds of particular interest are also those of the formulae (I) to (III) which are distinguished by the fact that they contain an acylamino group, especially NHCO-C1-C4-alkoxy. In this case, n preferably represents 3 and otherwise represents 4.

The new disazo dyestuffs are accessible by diverse processes.

One process is characterized in that the disazo dyestuffs of the formula

wherein A, B, C, I and m have the aforementioned meaning and Me represents a metal, preferably an alkali metal (especially Na and K), are partially or completely etherified or esterified, in a manner which is in itself known, with compounds of the formula Q-(E-O)n-R (ss/) wherein E, R and n have the abovementioned meaning and Q represents halogen, preferably Cl, or CH3-C6H4-SO3- or CH3S93e, and optionally, in the case of the partial reaction, the reaction product is then reacted with compounds D-Q (D = alkyl).

The compounds of the formula (V) are known or are easily accesssible by known methods (compare German Offenlegungsschrift 1,544,599, page 22), by, for example, oxyalkylating compounds of the formula ROH, subjecting the reaction product to fractional distillation, replacing the terminal OH group in the particular fractions by the radical Q (for example by reaction with SOCI2 or methanesulphonyl chloride) and if necessary distilling again, in order to remove decomposition products. Advantageously, however, the industrial oxalkylation products of ROH are used without fractionation.

Another variant for the preparation of the new polyether disazo dyestuffs consists in etherifying or esterifying disazo compounds of the formula

wherein A, B, C, Q, I and m have the abovementioned meaning and Q is bonded direct or via CO, with compounds of the formula R(OE),--OMe (ill) wherein R, E, Me and n have the abovementioned meaning. (Compare, for example, Japanese Patent Specification 48/71,267).

Finally, the new dyestuffs can be prepared by conventional diazotisation and coupling reactions, using corresponding starting materials which already contain the characteristic radicalO(EO)nR.

In this case, this radical is introduced in a manner analogous to that for the finished dyestuffs.

Dyestuffs and intermediate products which contain the radical O(EO)R, in which R rep resents acyl (preferably OCONV,V2), are appropriately prepared from the corresponding compounds which contain polyether groups and in which R = H, by reaction with corresponding acid anhydrides or acid halides or - as in the case of R = 0CONV1V2 - with isocyanates.

The new dyestuffs are outstandingly suitable for dyeing and printing synthetic fibre materials, especially those made of aromatic polyesters and cellulose esters, on which they produce dyeings with good general fastness properties, in particular good fastness to sublimation, washing and light.

It is particularly advantageous to use the dyestuffs in the form of liquid or pulverulent preparations which, in addition to the dyestuff, contain emulsifying polar-apolar compounds and also, optionally, diluents and extenders (especially inorganic salts, such as NaCI and Na2SO4).

These preparations are distinguished by very high solubility in cold water.

In general, a molar ratio of dyestuff to emulsifier of 1:0 to 1:4 has proved advantageous; a ratio of 1:1 to 1:3 is preferred and in general an excess of emulsifier is not harmful. In practice, however, a two-fold excess will in general be completely adequate.

The production of the dyestuff preparations is not tied in specific prerequisites in respect of apparatus. Spray-drying, roller-drying or drying in Venuleth apparatuses are just as suitable as simple drying on sheet metal, after combination of the components, in normal kettles, or the combination of adduct formation and drying in the abovementioned apparatuses. It is particularly advantageous to mix the filter press cake or the oily or pasty dyestuff in the form in which it is obtained directly from the preparation, with the emulsifiers and to convert the mixture to the dry, pulverulent form in a known manner. A fact to be singled out in this connection is that, should the dyestuff/emulsifier mixture be comminuted, no expensive equipment for producing a state of fine division, such as bead mills and vibratory mills, has to be employed, but coarse grinding to average particle sizes which are not below 50 y is wholly adequate.

A list of suitable emulsifiers is given in Table 1 in "Tenside Detergents", year 1 1, 1974, number 4, page 186.

Preferred polar/apolar compounds have the general formula G-L (VIII) wherein G represents an aliphatic hydrocarbon radical with at least 10 C atoms and L represents -SO 3H, -O-SO3H or OPO3H2 or the corresponding salts.

Examples which may be mentioned are: fatty acid soaps, such as sodium laurate, sodium oleate, sodium linoleate, ammonium ricinoleate, oleic acid esters of sodium isethionate or sodium palmitate, sodium bis-(2-ethylhexyl)-sulphosuccinate, sodium N-methyl-N-oleyl-taurate, -(tert.-ocwlphenoxy)- diethyl ether P'-Na-sulphonate, sodium isododecylbenzenesulphonate, sodium dodecyl-sulphate, sodium N-oleyl-sulphanilate, dodecyl-phosphonic acid, sodium dodecylbenzimidazolesulphonate, alkoxyaryl sulphates, alkylsulphaminoaryl compounds, dodecylphenol sulphate, dodecylbenzenesulphamic acid, dibutylnaphthol sulphate and dioctylnaphthol sulphate. Cationic surface-active agents which may be mentioned are dodecylamine acetate, dodecylbenzyldimethylammonium chloride and heptadecyl-N-(aminoethyl)-imidazoline acetate.

Under dyeing or printing conditions, the new dyeing preparations are in a liquid or dissolved form.

As a result of this, the use of additional surface-active agents, such as dispersing agents, protective colloids or levelling agents, or of carriers can in most cases be dispensed with when dyeing and printing.

In the examples which follow, "parts" denote parts by weight.

EXAMPLE 1 399 parts of the dyestuff of the formula

in the form of the dry, industrial and finely ground product, are introduced into 289 parts of the compound of the formula Cl (C2H40)3~5CH3 at 900 C, whilst stirring. 882 parts of concentrated sodium hydroxide solution (45% strength) are then added dropwise in the course of 3 hours at 100 to 11 OOC. After stirring for a further 10 hours at this temperature, the reaction product is stirred into 6,000 parts of water, filtered off and washed with water The resulting paste is stirred into 1,750 parts of a 30% strength aqueous solution of myristyl alcohol sulphate at 600C and stirring is continued at 80 to 850C, with the addition of an aqueous solution of 200 parts of sodium sulphate, until everything has dissolved (about 7 hours). The resulting solution is converted by spray-drying to a powder, which is readily soluble in water. If this powder is employed in the conventional manner for dyeing polyester fibres, a yellowish-tinged orange dyeing with good fastness properties, in particular good fastness to rubbing, is obtained.

If the emulsifier used in the preparation of the dyestuff paste, described above, is replaced by 1.5 mols (based on dyestuff) of dodecyldimethylbenzylammonium chloride or by 1.5 mols of oxethytated oleyl alcohol (degree of oxethylation 19), pastes which dissolve rapidly in warm water and can be used in the customary manner for dyeing polyester fibres are again obtained.

EXAMPLE 2 190 parts of the dyestuff of the formula

in the form of the industrial dry product, are dissolved in a solution of 22 parts of sodium hydroxide in 500 parts by volume of methanol, whilst stirring. The methanol is then distilled off in vacuo. 200 parts of the compound of the formula Cl(C2H4O)3sCH3 are added to the residue and the mixture is heated at 1 00C for 7 hours, whilst stirring. The reaction mixture is introduced into 4 1 of water and the resulting mixture is stirred overnight at pH 10. The product is then filtered off and washed until salt-free.The paste thus obtained (about 890 g) is introduced into 900 parts of an aqueous 30% strength solution of myristyl alcohol sulphate at 600 C, whilst stirring, and the mixture is heated for about 7 hours at 80 to 850C and at pH 5-6 until the solution is clear on dilution with water. After stirring in 200 parts of sodium sulphate, the concentrated aqueous solution is converted to a dry powder by spray-drying. This powder dissolves rapidly in water.

When used in the customary manner for dyeing polyester fibres, it produces a yellowish-tinged orange dying with good fastness to rubbing. If the same procedure is followed, but the following compounds are employed: Cl(C2H40)sH, CI(C2H4O)3 CONHCH3,

dyestuffs with similar properties are obtained.

The dyestuffs which are listed in the table which follows and which likewise can easily be dissolved or emulsified in aqueous dyebaths without involved formulation procedures are obtained in ana!ogous manner.

Example Dyestuff Colour shade 3 CC130CC;rH40)30N=N- N=No(e24P)3cH3 yellow 4 Cz3Co 9=s < t4 < 3Cn0C2.ss-Fo)5 < 5 N : occ4o) 5 S orange c3 5 CR3Cclt4H e 8 0C2M46 gC295 orange 6 CHJCONCIe-= orange C"3 7 C cot4"ra 3 (C 4 )4coN4CS N orange 8 oaN < 3r4=N < s < N-NOCC2CI00)3CMHCS orange C"3 9 C"'3Cc,N" N N, N oCca 4O3CoN ca orange CI CH3 10 CU3CON O9=9 v43 orange ca OCCBH40)3CONHC"3 11 024 < s-N < r4-r4 < C)(CZE40)5CH3 orange C"3

Example Dyestuff Colour shade 12 /\::N /\ 3,8C3 reddi reddish-tinged - - - yellow cCCO4- C4q 13 /\ N--N- M -N reddish-tinged - - - yellow Ca5 14 cH3-o r\L=N-~o(CrH40)4CU reddish-tinged yellow cw3 15 H5C214NCO(3C)30ON 3O(C2!4O)3CON9CZAS orange Ct 16 (Ow3C)o < N=s QO6c2H4o 3cFx3 orange Cl c1 c*3 17N=N yellow oCca4ooCak5 reddish-tinged 043 yellow 18 reddish-tinged 18 Cij-C-r4 / reddish-tinged yellow CFT3 19 N=N orange o6C2l 4o 5Co9tZF CH3 CW3 oaN > ~O(C2Fo40)±* > CZ95 orangeorange C"3

Example Dyestuff Colour shade 21 O;rN-e ; red-brown cs cS 22 02t4 < s=N9 9Oo(c2Ft4o)4cu3 orange OCH 5 23 9 O o(C2H403CWJ orange CH3 o-cLa oC44a 24 et 4eo(C2,40)3 & scarlet o- oFt3 c93 25 HsC(OC2H4)3-0 < tN N:N 9 O(C2H40)3CoCw3 reddish-tinged yellow CH3 c 3 OsCC2Fl40)5C3 26 QNtN-73 N=N reddish-tinged yel low CR3 CH3 27 OaN N-N N::N o(C2o4coctlaocLa orange o-crg 28 Cs6OC2Hv)2 goN-9 Oo(ci44 )3-8C & 3 yellow OCH 29 02|4Os-s < s -o(C2940)4cl43 red-brown c43

Example Dyestuff Colour shade 3 30 0#4t 3oCct^)3~5C3 orange 31 o24 < s sOo(cP*ci)3Ft orange 32N=N- 3O6c23OsCn(cl4332 orange OCH3 33 OIc2H40)3-4H orange OCH3 CH3 ~ICH3=r*l- CH3 34.N--N-( red 35 r'l O FS:N-8, C1 red < 502-s-C3%O(CtFt4C93C3*5 38 N : 3- N 5 j-7CZS red t coo(c )3-7CZS 37 N3.NN-N C red 043 Ce3 38 (C%)2N-So2 < 314-t4 < 0(C240)3C3 orange O-C3

Example Dyestuff Colour shade "" oh 38a ;" orange CH3 Cl42CH2 CooCczH40)3CH3 39 Cl43t) t3 CW30N=N sC'\ orange cb4a 40 OZO4 ON~N < s~NC30IC2.w)4C NHCE3 orange NoC$3 41 NCX ly=N CUr2)46(Cw3)40 (CZH4P)4Q13 orange cl CH3 42 CCo::N X H3 S3C2H4C)6C4g9 orange CH3 43 CH3 (C294 )5C0 t39=N O O 3 orange 44 c4149o6czFI4 )sco < N-N < Ft orange 024 < 3N- < orange 6C2H 40) 5C * Hv 46 0a < C 3 orange C)6C2Ft40)5CHt

Example Dyestuff Colour shade oCttL 47oCCZH40)4CONH orange 48 ON~9 =N 42occ240ba7c3l47 orange 48 49 C6oco N : Ca: 30(c2 40)3 Sc*43 scarlet och3 50 29 N--N- 3O(C244*OD34C2Fl5 orange Cl 51 CHso- N -N N=N- Cp*+O)ss*i reddish-tinged yew low ctt3 52 CH30CC2H4 93 OCH3 J < N=SX30CH3 yellow Ct 53 Ch30 o = N 914N < 3 0 yellow 3 54 cw30-N=N-N-N- CH CaW40)qCZWS.CI yellow 55 CH30 < h1 = N < N=(rlOICZn90)5CONHC2H4C' yellow cg3

Example Dyestuff Colour shade 56 OCc,H4E,)4-6CONi 5 4306cz > t4 > 4-Gbcos84c2S 5 orange 6CH 57 CF3o~N < s~NUO(CZU40)b~5C SH2 scarlet ocng

EXAMPLE 58 1 9.7 parts of aminoazobenzene are dissolved in 60 parts of glacial acetic acid and 50 parts of concentrated hydrochloric acid. 1 50 parts of ice are added to this solution and, whilst stirring, 7 parts of sodium nitrite in 30 parts of water are also added at OOC. After about one hour, a solution of 38 parts of the salicylic acid ester of the formula

in 60 parts of glacial acetic acid is added. Whilst cooling, concentrated sodium hydroxide solution is added dropwise at OOC until no further diazonium salts are present. The pH is then adjusted to 5 and the dyestuff which has precipitated is separated off and mixed to a paste with fatty alcohol, sulphates, as in Example 1. After spray-drying, a powder is obtained which is readily soluble in warm water and is outstandingly suitable for dyeing polyester fibres.

The salicylic acid ester employed can be obtained in a conventional manner from salicylic acid chloride by reaction with a corresponding polyether-alcohol.

EXAMPLE 59 7 parts of sodium nitrite (dissolved in 30 parts by volume of water), are allowed to run dropwise, at below 50C, into a mixture of 200 parts of water and 300 parts by volume of concentrated hydrochloric acid with 35 parts of the compound of the formula

and 200 parts of ice. The resulting mixture is stirred for a further 1 5 minutes and 11 parts of m-toluidine (dissolved in 25 parts by volume of glacial acetic acid) are then added. The reaction mixture is buffered to pH 3 with sodium acetate and stirred for a further 1 5 minutes. 40 parts by volume of concentrated hydrochloric acid are now added and a further 7 parts of sodium nitrite (dissolved in 30 parts by volume of water) are allowed to run dropwise into the resulting solution, at below 50C. The mixture is stirred for a further 1 5 minutes and 10 parts of phenol (dissolved in 200 parts of water and 10 parts of glacial acetic acid) are then added. The mixture is then neutralised with concentrated sodium hydroxide solution at below 1 OOC and the dyestuff of the formula

precipitates out. The dyestuff is filtered off, washed with water and processed, as in Example 1, with emulsifiers to give a dyestuff preparation.

Claims

1. Disazo dyestuffs which are free from sulphonic acid groups and ammonium groups and have the formula

wherein D represents H, alkyl or --(EE-O)),-R, E represents alkylene, R represents H, alkyl, cycloalkyl, aralkyl, aryl or acyl, n represents 3 to 7, m represents 1 or 2 and I represents 0 or 1 and the said radicals and also the benzene rings A, B and C, which are optionally made up to naphthalene ring systems, can be substituted by non-ionic radicals customary in the chemistry of the azo dyestuffs and/or by COOH, with the proviso that at least one radical D represents -O-(EO)n-R.

2. Dyestuffs according to Claim 1, characterised in that the radicals-OD and -C02D are bonded to one and the same nucleus.

3. Dyestuffs according to Claim 1, of the formula

wherein E, R and n have the meaning indicated in Claim 1 and T represents H or a non-ionic substituent or COOH and r represents 1 to 3.

4. Dyestuffs according to Claim 1, of the formula

wherein X represents H, C1-C4-alkyl, C1-C4-alkoxy, OH, NO2, CN, CF3, F, Cl, Br, C1-C4- alkylcarbonylamino, C1-C4-a Ikoxycarbonylamino, p-hydroxyethyl or Y, represents H, C1-C4-alkyl, C1-C4-alkoxy or CI, Y2 represents Y, or NHCO-C1-4-alkyl, or together with Y represents a fused benzene nucleus, Y3 represents Y1, Z represents Y1, p represents 1 or 2, n' represents 3 to 5, R' represents C1-C4-alkyl or -CONV1V2, in which V, and V2 denote H or C1-C2-alkyl, and E' represents C2H4 or -(CH2)4-.

5. Dyestuffs according to Claim 4, characterised in that X represents H, CH3,OCH3, OC2Hs, OH, NO2, CH3CONH, CH30CONH, C2H5-OCONH or Cl; Y, represents H; Y2 and Y3 represent CH3, H, OCH3 or Cl; Z represents H, CH3 or Cl; R' represents CH3 or C2H5 and E' represents H2CH2-.

6. Dyestuff according to Claim 1, of the formula

7. Process for the preparation of disazo dyestuffs according to Claim 1, characterised- in that disazo dyestuffs of the formula

A, B, C, I and m have the meaning indicated in Claim 1 and Me represents a metal, preferably an alkali metal are etherified or esterified, in a manner which is in itself known, with compounds of the formula Q-(E-O)n-R (V, wherein E, R and n have the meaning indicated in Claim 1 and 0 represents halogen, CH3CeH4SOa or CH3SO3e.

8. Dyestuff preparations containing a dyestuff according to Claim 1 and also a polar/apolar emulsifying compound.

9. Process for dyeing qr printing synthetic fibre materials, characterized in that dyestuffs according to Claim 1 or dyestuff preparations according to Claim 8 are used.